Sealant compositions and method of producing the same

ABSTRACT

A sealant composition for the puncture-sealing tire and a method of producing the same are disclosed. This sealant composition is crosslinking-reaction type and comprises (A) at least one rubber, (B) a tackifier, (C) an acryloyl or methacryloyl group-containing polymerizable unsaturated compound, (D) a filler and (E) a photopolymerization initiator. In the production of the sealant composition, the component (A) is first reacted with the component (C) and then kneaded with the components (B), (D) and (E).

This is a continuation of application Ser. No. 490,085, filed Apr. 29,1983, now U.S. Pat. No. 4,548,687.

This invention relates to a crosslinking-reaction type sealantcomposition for a puncture-sealing tire, which can prevent the leakageof air filled in a tire even when puncturing objects scattered on roadsurface such as nails and a like pass through a tread portion of thetire during the running thereof, and a method of producing the same.

Based on the idea that a tacky rubber layer prevents the leakage offilled air by sealing against a puncturing object even when thepuncturing object passes through a tread portion of the tire during therunning thereof, and that even when the puncturing object is removed outfrom the tread portion by centrifugal force based on the rotation of thetire during the running thereof, the tacky rubber sealant flows into thepuncturing hole and retains airtightness of the tire, manypuncture-sealing pneumatic tires which comprise a thin rubber layerhaving a tackiness as a sealant for the prevention of tire puncture onits inner surface have been manufactured. However, satisfactoryperformances have not yet been obtained since besides the performance ofsealing against the puncturing object, the sealant flows into andunevenly accumulates near the center of the tread due to the heatbuild-up of the tire, the viscosity of the sealant is reduced due totemperature rising, and the tire balance is lost and the safety isreduced due to centrifugal force caused by rotation of the tire. On theother hand, if it is intended to make the sealant hard in order toreduce the flowability, the sealant has a tendency of reducing thetackiness performance against the puncturing object. Moreover, when thetire provided with such a sealant is left to stand outdoors withoutmounting on a rim of a wheel, the sealant absorbs water such as rain orthe like and causes reduction of tackiness. As a result, the sealant isstriped from the inner surface of the tire during the running thereof.

In order that a sealant for the prevention of puncture practicallymaintains satisfactory performances, such a sealant must not only has anexcellent tackiness and no fluidity phenomenon but also must satisfyvarious requirements such as maintenance of expected performances athigh and low temperatures, low water absorption, no oxidativedegradation by air under high temperature and pressure, no bad influenceupon material of each part constituting the tire and the like. In orderto develop such performances, there have hitherto been proposed variousmethods. For instance, there are typically (1) a method wherein aperoxide-crosslinking type sealant composition is dissolved in a solventand then sprayed into the inner surface of the tire under heating, (2) amethod wherein a two layer structure of an inner liner and a sealantlayer located thereinside is formed in the tire building, (3) a methodwherein a sealant layer is applied to the inside of the tire and furthera hard and fluidity-resistant material is applied thereon as a cover,and the like. All of materials obtained by these conventional methodsare fairly excellent in fluidity resistance, but have some drawbacks.That is, in method (1), solvent is used for the spraying, so that theworking atmosphere becomes contaminated such that in the production stepa composition containing a peroxide has a very short pot life. In method(2), the application of the sealant layer is difficult in the tirebuilding, so that it is necessary to reduce the sealing property to acertain extent in order to make such an application possible, whilethere are manufacturing and technical problems such as foaming oftackifier or the like in the sealant composition and so on due to hightemperature at vulcanization. Further, method (3) is fairly improved ascompared with methods (1) and (2) but has a problem in productivityowing to the necessity of at least two steps for application of sealant.Moreover, when the hard layer exists in the inside of the tire asdescribed in methods (2) and (3), there is a tendency of somewhatreducing the sealing property after the pulling out of puncturingobjects such as nail or the like.

The inventors have made various studies with respect to the developmentof sealant compositions eliminating the aforementioned drawbacks of theprior art, satisfying various requirements as a sealant for theprevention of tire puncture, having a good productivity and notcontaminating the working atmosphere by solvent and the like, and as aresult the invention has been accomplished. That is, the sealantcomposition according to the invention is a crosslinking-reaction typeand comprises (A) at least one rubber selected fromethylene-propylene-diene terpolymer rubber, butyl rubber, halogenatedbutyl rubber and conjugated diene butyl rubber, (B) a tackifier, (C) anacryloyl or methacryloyl group-containing polymerizable unsaturatedcompound, (D) a filler and (E) a photopolymerization initiator.Furthermore, the invention lies in a method of producing sealantcompositions, which comprises reacting (A) at least one rubber selectedfrom ethylene-propylene-diene terpolymer rubber, butyl rubber,halogenated butyl rubber and conjugated diene butyl rubber with (C) anacryloyl or methacryloyl group-containing polymerizable unsaturatedcompound in the presence of an alkylhypohalite to produce a polymerhaving an α,β-unsaturated carboxylate group represented by any one ofthe following general formulae: ##STR1## wherein X is a halogen atom,each of R¹, R² and R³ is a hydrogen atom or a hydrocarbon residuecontaining 1 to 10 carbon atoms, n is an integer from 2 to 5, m is aninteger from 1 to 4 and l is an integer from 1 to 30; and kneading theresulting polymer with (B) a tackifier, (D) a filler and (E) aphotopolymerization initiator.

According to the invention, the component (A) may optionally be selectedfrom at least one of ethylene-propylene-diene terpolymer rubber, butylrubber, halogenated butyl rubber and conjugated diene butyl rubber, eachbeing produced by the conventional method.

As component (B), use may be made of one or more of liquid tackifierssuch as liquid polybutene, liquid polyisobutylene, liquid polypentene,liquid polyisobutylene-isoprene, liquid polyisobutylene-butadiene andthe like, or petroleum hydrocarbon resin tackifiers such as aliphaticpetroleum resin, aromatic petroleum resin, alicyclic petroleum resin andthe like, or natural tackifiers.

As component (C), use may be made of one or more compound selected fromacrylic acid, methacrylic acid and derivatives thereof. In general, thederivatives of acrylic or methacrylic acid are esters and amides. Analcohol residue of the ester includes, for example, cyclohexyl group,tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group,3-hydroxyethyl group and the like in addition to alkyl groups such asmethyl group, ethyl group, dodecyl group and stearyl group. Furthermore,there may be used esters of acrylic acid or methacrylic acid withethylene glycol, triethylene glycol or polyethylene glycol. On the otherhand, acrylamide and N-diacetonacrylamide may be used as an amide.

As component (D), use may be made of silica (white carbon), clay, mica,glass short fiber and the like.

As component (E), use may be made of at least one initiator forultraviolet light selected from benzoin, benzophenone, benzoin ethylether, benzoin isopropyl ether, dibenzyl, benzyldimethyl ketal,azobisisobutyronitrile, diacetyl and the like. Moreover, mention may bemade of combinations of N,N-dimethylaminobenzaldehyde/1,2-benzanthraquinone, Micheler's ketone/camphorquinone,methylene bisdimethylaniline/benzyl and the like as an initiator forvisible light.

In the sealant composition, 90 to 65 parts by weight of the component(B) is mixed with 10 to 35 parts by weight of the component (A) andfurther not more than 10 parts by weight of the component (C), 5 to 30parts by weight of the component (D) and not more than 10 parts byweight of the component (E) are added to 100 parts by weight of a totalof the components (A) and (B). According to the invention, when theamount of the component (A) is less than 10 parts by weight, thefluidity resistance is poor, while when it exceeds 35 parts by weight,the sealing property is poor. Particularly, the amount of component (A)is preferable within a range of 15 to 30 parts by weight, so that theamount of component (B) is preferable within a range of 85 to 70 partsby weight. Furthermore, component (D) is preferably used in an amount of10 to 20 parts by weight per 100 parts by weight of a total ofcomponents (A) and (B). When the amount of component (E) exceeds 10parts by weight, the light transmission property becomes poor. Thepreferable amount of component (E) is not more than 5 parts by weight.

In order to improve the storage stability, not more than 5% by weight ofa well-known polymerization inhibitor may be added to the sealantcomposition. As the polymerization inhibitor, mention may be made ofhydroquinone, hydroquinone monomethyl ether, p-benzoquinone and thelike.

The sealant composition according to the invention is produced bykneading the above mentioned components by means of a roll mill,kneader, Banbury mixer, extruder or the like. In the case of the polymerhaving an α,β-unsaturated carboxylate group, it is better that component(A) is first reacted with component (C) and then the resulting polymeris kneaded with components (B), (D) and (E). That is, a rubber of thecomponent (A) is reacted with an acryloyl or methacryloylgroup-containing polymerizable unsaturated compound of component (C)such as acrylic acid or methacrylic acid in the presence of analkylhypohalite such as t-butylhypochlorite or the like to produce apolymer having an α,β-unsaturated carboxylate group represented by anyone of the following general formulae: ##STR2## wherein X is a halogenatom, each of R¹, R² and R³ is a hydrogen atom or a hydrocarbon residuecontaining 1 to 10 carbon atoms, n is an integer from 2 to 5, m is aninteger from 1 to 4 and l is an integer from 1 to 30.

When the sealant composition according to the invention is used to forma puncture preventive layer for a tire, it may be dissolved in a solventand applied to an inner surface of the tire. However, it is preferablethat the sealant composition is heated to make its viscosity low andcoated on the inner surface of the tire as a coating layer having adesired thickness of, for example, about 1.5 to 4.0 mm by means of adoctor knife. In the latter case, the heated sealant composition is highin the tackiness, so that it can be applied to the inner surface of thetire without wiping out a talc from the inner surface of the tirebecause it is usually required to clean the inner surface of the tire.Thereafter, the crosslinking reaction is carried out by irradiating alight. As a light source, mention may be made of ones having an emissionwavelength at visible-ultraviolet region, such as high pressure mercurylamp, mercury-xenon lamp, halogen lamp, chemical lamp and the like.

Furthermore, the sealant composition can be fabricated into apredetermined shape by means of a press, T-die, extruder or the like.The thus shaped sealant is crosslinked by irradiating a light on arelease paper, which can be applied to the inner surface of the tire. Inthe formation of the sealant layer inside the tire, the above mentionedmounting method or doctor knife coating method does not degrade theworking atmosphere at the production stage as compared with the usuallyused method of dissolving the sealant composition in the solvent andspraying it, and has a very long pot life because the crosslinkingreaction does not occur until the irradiation of light.

The sealant composition according to the invention exhibits satisfactoryperformances at a single layer structure, and is simple in theproduction step and excellent in the tackiness, and forms a networkstructure by polymerization reaction under the irradiation of light tocompletely prevent the movement even at high temperature.

That is, the sealant composition crosslinked under the irradiation oflight has a viscosity of 5×10³ -5×10⁴ poises at a temperature of 80° C.and a shearing speed of 100 sec⁻¹ and is very rich in the tackiness andhas a crosslinked structure, so that it is low in the temperaturedependence of viscosity and does not exhibit the movement even at hightemperature. Further, the conventional sealant is high in the waterabsorption due to the absence of the network structure, while accordingto the invention the water absorption of the filler is restrained to alow value owing to the crosslinked structure of the sealant.

The invention will be described in detail with the following example.

EXAMPLE

(1) In a kneader were thoroughly kneaded 200 g of conjugated diene butylrubber (made by Exon Co., Ltd.), 600 g of polybutene 300 R (made byIdemitsu Sekiyu Kagaku K.K.), 96 g of silica (VN-3, made by NipponSirika K.K.), 16 g of dimethacrylic acid 1,3-butylene (made byMitsubishi Rayon K.K.), 6.4 g of benzoin ethyl ether (made by SeikoKagaku K.K.) and 3.2 g of 2,6-di-t-butyl-p-cresol (made by Seiko KagakuK.K.). The viscosity of the resulting composition was 5.5×10³ poises asmeasured at a temperature of 80° C. and a shearing speed of 100 sec⁻¹.This composition was called as a sealant A.

(2) In a kneader were thoroughly kneaded 160 g of brominated butylrubber (made by Exon Co., Ltd.), 640 g of polybutene 300 R, 96 g ofsilica, 24 g of trimethylol propane triacrylate (made by ShinnakamuraKagaku K.K.), 6.4 g of benzoin isopropyl ether and 3.2 g of2,6-di-t-butyl-p-cresol. The viscosity of the resulting composition was2.8×10³ poises at a shearing speed of 100 sec⁻¹ and 1.0×10⁴ poises at ashearing speed of 10 sec⁻¹ as measured at a temperature of 80° C. Thiscomposition was called as a sealant B.

(3) 200 g of conjugated diene butyl rubber was masticated by means of aroll mill at a temperature of 50° C., to which was added dropwise 5.8 gof methacrylic acid (one molecule per molecular weight of conjugateddiene butyl rubber of 3,000) and further added 7.3 g of t-butylhypochlorite (equimolar amount per methacrylic acid). The resultingmixture was kneaded for 10 minutes to obtain a modified conjugated dienebutyl rubber. After the completion of the reaction, the rubber wasdissolved in toluene and poured into methanol, from which a precipitatedpolymer was taken out and dried and then dissolved in toluene. Theinfrared ray absorption spectrum of the resulting solution showed wavenumbers of 1,710 cm⁻¹ assigned to carbonyl group and 1,160 cm⁻¹ assignedto ester group.

In a kneader were thoroughly kneaded 200 g of the modified conjugateddiene butyl rubber, 600 g of polybutene 300 R, 96 g of silica, 6.4 g ofbenzoin isopropyl ether and 3.2 g of 2,6-di-t-butyl-p-cresol. Theviscosity of the resulting composition was 2.8×10³ poises at a shearingspeed of 100 sec⁻¹ and 8.2×10² poises at a shearing speed of 1,000 sec⁻¹as measured at a temperature of 100° C. This composition was called as asealant C.

PROPERTY TEST

Each of the above three sealants was passed through a vent tuber heatedat 50° C. to remove air bubbles from the sealant and coated on an innersurface of a tire (steel belt radial tire of a size 165-SR-13, made byBridgestone Tire Co., Ltd.) as a sealant layer having a width of 11 cmand a thickness of 3 mm by means of a doctor knife heated at 100° C. Thesealant layer was crosslinked so as to obtain a predetermined viscosityby irradiating a light to the inner surface of the tire with a highpressure mercury lamp. As the viscosity was measured at 100° C. afterthe crosslinking, the sealant A was 1.3×10⁵ poises at a shearing speedof 10 sec⁻¹ and 2.2×10⁴ poises at a shearing speed of 100 sec⁻¹, asealant B was 7.0×10⁴ poises at the shearing speed of 10 sec⁻¹ and1.3×10⁴ poises at the shearing speed of 100 sec⁻¹, and the sealant C was1.0×10⁵ poises at the shearing speed of 10 sec⁻¹ and 2.0×10⁴ poises atthe shearing speed of 100 sec⁻¹. The following tests were made withrespect to the puncture-sealing tires obtained by the above method.

(1) Fluidity test of sealant during high-speed running

Each of the above three tires was assembled into a rim and inflated toan internal pressure of 2.7 kg/cm², which was run on a test drum at aspeed of 140 km/hr under a load of 225 kg for 2 hours. Thereafter, thetire was disassembled from the rim and then the fluid state of thesealant was examined. As a result, all of the sealants A-C held theoriginal state before running without causing movement.

For the comparison, three tires were manufactured in the same manner asdescribed above except that the sealant was not exposed to a light andthen subjected to the same test as described above. In this case, thesealant exhibited significant movement toward the central portion at theinner surface of the tire.

(2) Sealing property during the running at a nailed state

Each of the same three tires as used in the test (1) was again assembledinto a rim and inflated to an internal pressure of 1.7 kg/cm². Then, 24nails were inserted in tread center region and shoulder region of thetire at block portion and groove portion of tread pattern so as topenetrate into the inside of the tire by using three kinds of ironnails, first kind of which having a diameter of 2.4 mm and a length of51 mm, second kind of which having a diameter of 2.7 mm and a length of64 mm, and third kind of which having a diameter of 3.4 mm and a lengthof 76 mm. After these tires were left to stand for a given time, a soapsolution was applied to the nailed portions to examine air leakage fromthe nailed portion. As a result, the air leakage was not observed in allof the three tires and the sealing property was perfect.

Then, each of these three tires was run on a test drum at a speed of 60km/hr under a load of 360 kg over a distance of 1,500 km. After therunning, the tire was taken out from the drum and left to stand for sometime, during which the internal pressure was measured and the initialinternal pressure of 1.7 kg/cm² was confirmed to be maintained withoutchange. Furthermore, the air leakage from the nailed portion was notobserved by testing with the soap solution. Moreover, even when all thenails were pulled out from the tire, there was observed no air leakagefrom puncturing-holes because these holes were completely sealed withthe sealant.

(3) Water absorbing property of sealant

The sealant A or B was shaped into a specimen of 30×30×3 mm, mounted toa stainless steel net and crosslinked by the irradiation of a mercurylamp. These specimens were immersed in a distilled water at roomtemperature for 10 days and then the water absorption thereof wasmeasured. As a result, the crosslinked sealant A had a water absorptionof 2.5% by weight, while the crosslinked sealant B had a waterabsorption of 1.5% by weight, so that both the sealants hardly absorbedwater. On the other hand, the water absorptions of the sealants A and Bbefore crosslinking were 13% by weight and 3.0% by weight, respectively.

As apparent from the above results, the sealant compositions accordingto the invention are crosslinked by light irradiation and developsatisfactory performances as a sealant for tire.

What is claimed is:
 1. A crosslinking-reaction type sealant compositionfor a puncture-sealing tire comprising: (A) a halogenated butyl rubber,(B) a liquid polybutene as a tackifier, (C) an acryloyl or methacryloylgroup-containing polymerizable unsaturated compound, (D) a filler and(E) a photopolymerization initiator, wherein 90 to 65 parts by weight ofcomponent (B) is mixed with 10 to 35 parts by weight of component (A)and then not more than 10 parts by weight of component (C), 5 to 30parts by weight of component (D) and not more than 10 parts by weight ofcomponent (E) are added to 100 parts by weight of a total of components(A) and (B).
 2. The crosslinking-reaction type sealant composition asclaimed in claim 1, wherein said acryloyl or methacryloyl groupcontaining polymerizable unsaturated compound (C) is selected from thegroup consisting of acrylic acid, methacrylic acid, esters of acrylicacid, esters of methacrylic acid, amides of acrylic acid, and amides ofmethacrylic acid.
 3. The crosslinking-reaction type sealant compositionas claimed in claim 1, wherein said filler (D) is selected from thegroup consisting of silica, clay, mica, and glass short fiber.